CN1302070C - Flame-retarded epoxy composition for packing semiconductor and semiconductor device - Google Patents
Flame-retarded epoxy composition for packing semiconductor and semiconductor device Download PDFInfo
- Publication number
- CN1302070C CN1302070C CNB031602789A CN03160278A CN1302070C CN 1302070 C CN1302070 C CN 1302070C CN B031602789 A CNB031602789 A CN B031602789A CN 03160278 A CN03160278 A CN 03160278A CN 1302070 C CN1302070 C CN 1302070C
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- China
- Prior art keywords
- epoxy resin
- composition
- epoxy
- resins
- phosphazene compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 239000004065 semiconductor Substances 0.000 title claims abstract description 20
- 239000004593 Epoxy Substances 0.000 title claims description 35
- 238000012856 packing Methods 0.000 title description 4
- 239000003822 epoxy resin Substances 0.000 claims abstract description 65
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 65
- -1 phosphazene compound Chemical class 0.000 claims abstract description 50
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 claims abstract description 11
- 150000001463 antimony compounds Chemical class 0.000 claims abstract description 11
- 238000005538 encapsulation Methods 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 239000012764 mineral filler Substances 0.000 claims description 21
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000005011 phenolic resin Substances 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 229940085991 phosphate ion Drugs 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000002075 main ingredient Substances 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 abstract description 38
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 28
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 150000001649 bromium compounds Chemical class 0.000 abstract 1
- 239000011256 inorganic filler Substances 0.000 abstract 1
- 229910003475 inorganic filler Inorganic materials 0.000 abstract 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 238000000465 moulding Methods 0.000 description 11
- 238000003825 pressing Methods 0.000 description 11
- 229920003987 resole Polymers 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- 230000031709 bromination Effects 0.000 description 8
- 238000005893 bromination reaction Methods 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910017083 AlN Inorganic materials 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 150000004693 imidazolium salts Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- SBGKCOJQKBHFTO-UHFFFAOYSA-N (2-nonylphenyl)phosphane Chemical compound CCCCCCCCCC1=CC=CC=C1P SBGKCOJQKBHFTO-UHFFFAOYSA-N 0.000 description 1
- HUCQPHINKBNKRU-UHFFFAOYSA-N (4-methylphenyl)phosphane Chemical compound CC1=CC=C(P)C=C1 HUCQPHINKBNKRU-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 150000001896 cresols Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- BVURNMLGDQYNAF-UHFFFAOYSA-N dimethyl(1-phenylethyl)amine Chemical compound CN(C)C(C)C1=CC=CC=C1 BVURNMLGDQYNAF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
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- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
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- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
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- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- QLAGHGSFXJZWKY-UHFFFAOYSA-N triphenylborane;triphenylphosphane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLAGHGSFXJZWKY-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
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Images
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-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Epoxy Resins (AREA)
Abstract
A flame retardant epoxy resin composition for semiconductor encapsulation includes as essential components, (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, and (D) a phosphazene compound of the average compositional formula (1) having a melting point of 110-130 DEG C., wherein a, b and n are numbers satisfying 0<a<=0.05n, 1.90n<=b<2n, 2a+b=2n, and 3<=n<=6, the composition being substantially free of bromides and antimony compounds.
Description
Technical field
The present invention relates to a kind of semiconductor packages fire retarded epoxy resin composition that is used for, although there is not bromide (for example, the Resins, epoxy of bromination) and antimony compounds (for example, antimonous oxide) exist, it still is suitable for mold pressing and is solidified into to have fire-retardant and the product moisture-proof reliability effectively.The invention still further relates to a kind of semiconducter device that encapsulates with the solidifying product of said composition.
Background technology
The semiconducter device of current main-stream has diode, transistor, unicircuit, large-scale integrated circuit and the super large-scale integration of resin package type.Resins, epoxy has superior moldability, adhesive performance, electrical property, mechanical property and wet fastness with respect to other thermosetting resin.Thereby use the composition epoxy resin encapsulated semiconductor device usually.Semiconducter device is used for each field of modern society now, for example, is used for electrical equipment and computer.In order to prevent to catch fire, require semiconducter device to have flame retardant resistance.
In order to improve flame retardant resistance, in the semiconductor encapsulating epoxy resin composition, generally include and antimonous oxide (Sb
2O
3) halogenated epoxy resin that combines.Halogenated epoxy resin and antimonous oxide are combined in has big radical-scavenging and air isolation effect in the vapor phase, thereby the effect that brings high flame retardant.
Yet halogenated epoxy resin produces toxic gas during burning, and antimonous oxide has powder toxicity.They have caused negative impact for HUMAN HEALTH and environment, wish to remove fully from resin combination these fire retardants.
Consider above-mentioned requirements, study, replace halogenated Resins, epoxy and antimonous oxide by utilizing oxyhydroxide (for example aluminium hydroxide and magnesium hydroxide) or phosphine flame retardant (as red phosphorus and phosphoric acid salt).Lamentedly, use these alternative compounds to cause various problems.Oxyhydroxide (for example aluminium hydroxide or magnesium hydroxide) has relatively poor flame retardant effect, therefore must add so that composition epoxy resin has flame retardant resistance with bigger amount.The viscosity of composition is increased to the deleterious degree of molding afterwards, causes molding defect for example space and wire distortion (wire flow).On the other hand, when semiconducter device was exposed in the hygrothermal environment, the phosphonium flame retardant (for example red phosphorus and phosphoric acid salt) that joins in the composition epoxy resin can hydrolysis produce phosphoric acid.The phosphoric acid that is produced causes aluminium conductor to be corroded, and reduces its reliability.
For addressing these problems, Japanese Patent No. 2,843,244 propose to use top layers to scribble Si
xO
yRed phosphorus as the composition epoxy resin of fire retardant, but it still lacks the moisture-proof reliability.Japanese Patent-A-10-259292 discloses a kind of composition epoxy resin, has wherein used cyclic phosphazene compound, and consumption is given 0.2-3.0wt% with phosphorus atom, based on the gross weight of other component except that filler.For flame retardant resistance is provided, must in composition epoxy resin, add a large amount of cyclic phosphazene compounds, in hot environment, may cause solidifying invalid and reduce resistance.
Summary of the invention
The purpose of this invention is to provide a kind of semiconductor packages fire retarded epoxy resin composition that is used for, although there is not bromide (for example, the Resins, epoxy of bromination) and antimony compounds (for example, antimonous oxide) exist, it still is suitable for mold pressing effectively and is solidified into the product with high flame retardant and moisture-proof reliability.Another purpose provides a kind of semiconducter device of cure states composition encapsulation.
We have found that the semiconductor packages fire retarded epoxy resin composition that is substantially free of bromide and antimony compounds, and moldable effectively have the product that improves flame retardant resistance and moisture-proof reliability with being solidified into, wherein this composition epoxy resin comprises (A) Resins, epoxy, (B) solidifying agent, (C) mineral filler, (D) fusing point of on average forming general formula (1) is 110 ℃-130 ℃ a phosphazene compound, shows below.Semiconducter device with the encapsulation of the composition epoxy resin of cure states is having improvement aspect flame retardant resistance and the moisture-proof reliability.
Therefore, the invention provides a kind of semiconductor packages fire retarded epoxy resin composition, it comprises as main ingredient:
(A) Resins, epoxy,
(B) solidifying agent,
(C) mineral filler and
(D) fusing point of the average general formula of forming (1) is 110-130 ℃ a phosphazene compound,
Subscript a wherein, b and n satisfy 0＜a≤0.05n, 1.90n≤b＜2n, and the number of 2a+b=2n and 3≤n≤6, said composition does not have bromide and antimony compounds basically.
Be the semiconducter device of this composition epoxy resin solidifying product of a kind of usefulness encapsulation also in this concern.
As mentioned above, composition epoxy resin of the present invention does not have bromide and antimony compounds basically.Though the Resins, epoxy of bromination and antimonous oxide are usually included in traditional composition epoxy resin to give flame retardant resistance, composition epoxy resin of the present invention does not rely on the Resins, epoxy of bromination and antimonous oxide to reach fire-retardant specification UL-94, V-0.
In the prior art, study, replace the Resins, epoxy and the antimonous oxide of bromination by utilizing oxyhydroxide (for example aluminium hydroxide and magnesium hydroxide) or phosphine flame retardant (as red phosphorus and phosphoric acid salt).Lamentedly, known have the common shortcoming for the alternate fire retardant, and promptly water tolerance is relatively poor, particularly at high temperature, so they are dissolved and decompose to increase the foreign ion in the extraction water.Therefore, if traditional semiconducter device that does not have the fire retarded epoxy resin composition encapsulation of bromide and antimony compounds is basically preserved one long-time in hygrothermal environment, the aluminium conductor in the device will be corroded so, reduce its moisture-proof reliability.
Based on above-mentioned consideration, we have found that and do not increase the semiconductor encapsulating epoxy resin of foreign ion in extraction water composition, moldable effectively and be solidified into and have the product that improves flame retardant resistance and moisture-proof reliability, wherein this composition epoxy resin fusing point of using average composition general formula (1) as 110-130 ℃ phosphazene compound as fire retardant (D).This phosphazene compound is very water-fast, and does not increase the foreign ion in the extraction water.
Description of drawings
Fig. 1 is phosphazene compound SPE-100 gel permeation chromatography (GPC) figure.
Fig. 2 is the GPC figure of phosphazene compound SPE-100 behind recrystallize.
Fig. 3 is phosphazene compound SPE-100 dsc (DSC) figure.
Fig. 4 is the DSC figure of phosphazene compound SPE-100 behind recrystallize.
Embodiment
The component of composition epoxy resin of the present invention (A) is a Resins, epoxy, and it is not critical, as long as it comprises at least two epoxy group(ing) in a molecule.The illustrative example of suitable Resins, epoxy comprises phenolic resin varnish type epoxy resin, the cresols phenolic resin varnish type epoxy resin, the triphenol alkane type epoxy resin, aralkyl-type epoxy resin contains the aralkyl-type epoxy resin of biphenyl backbone, biphenyl type epoxy resin, dicyclopentadiene type Resins, epoxy, heterocyclic ring epoxy resins, naphthalene-ring containing Resins, epoxy, bisphenol type epoxy compound, Bisphenol F type epoxy compounds and 1-2-toluylene type Resins, epoxy.These Resins, epoxy can use separately, and perhaps two or more are used in combination.The Resins, epoxy that does not comprise bromination.
The hydrolyzable cl content of Resins, epoxy used herein is preferably until 1,000ppm, and particularly until 500ppm, the content of sodium and potassium is respectively until 10ppm.If hydrolyzable cl content is greater than 1,000ppm, if or the content of sodium or potassium greater than 10ppm, when the semiconducter device of encapsulation is present in the hygrothermal environment for a long time, its wet fastness will reduce.
Component (B) is a solidifying agent, neither be critical.Usually resol is as solidifying agent.The illustrative example of typical case's phenolic resin curative comprises novolac resin, naphthalene-ring containing resol, aralkyl-type phenol resin, triphenol alkane type resol, the aralkyl-type phenol resin that contains biphenyl backbone, biphenyl type resol, alicyclic ring resol, heterocycle resol and bisphenol type resol, for example dihydroxyphenyl propane and Bisphenol F type resol.These resol can use separately, and perhaps two or more are used in combination.
The same with Resins, epoxy, the content of solidifying agent sodium used herein and potassium is preferably respectively until 10ppm.If the content of sodium or potassium is greater than 10ppm, when the semiconducter device of encapsulation is present in the hygrothermal environment for a long time, its wet fastness will reduce.
The amount of the solidifying agent that uses not is a key, needs only its effectively cured epoxy resin.When the solidifying agent that uses is resol, in the employed solidifying agent in phenolic hydroxyl group and the Resins, epoxy mol ratio of epoxy group(ing) be preferably 0.5-1.5,0.8-1.2 more preferably.
In practice of the present invention, preferably use the curing reaction between curing catalyst promotion Resins, epoxy and the solidifying agent.Curing catalyst can be the material of any suitable promotion curing reaction.The non-limiting example of operable curing catalyst illustrative comprises for example triphenylphosphine of phosphine compound, tributylphosphine, three (p-methylphenyl) phosphine, three (nonyl phenyl) phosphine, triphenylphosphine triphenylborane and tetraphenyl phosphine tetraphenyl boric acid ester; The tertiary amine compound is triethylamine for example, phenmethyl dimethylamine, Alpha-Methyl phenmethyl dimethylamine and 1,8-diazabicylo [5.4.0] undecylene-7 (DBU); With imidazolium compounds for example glyoxal ethyline, 2-phenylimidazole and 2-phenyl-4-methylimidazole.
With the curing reaction between mixing cured promotor promotion Resins, epoxy of significant quantity and the solidifying agent (being generally resol), it desirably is amount with per 100 parts by weight of component (A), (B) and the about 0.1-5 weight part of mixture (D), more desirably be to mix with the amount of about 0.5-2 weight part, and whether be aforesaid phosphorus compound with it, tertiary amine compound or imidazolium compounds are irrelevant.
The mineral filler (C) that is included in the composition epoxy resin of the present invention can be that any one is generally used for the suitable mineral filler in the composition epoxy resin.Illustrative example comprises silicate (for example fused silica and crystalline silica), alumina, silicon nitride, aluminium nitride, boron nitride, titanium dioxide and glass fibre.
Though mean particle size and shape to these mineral fillers do not have particular determination, special preferred average particle size is the spherical fused silica between the 5-30 μ m.
The amount of the mineral filler that loads is not crucial.For improving flame retardant resistance, the mineral filler that is included in the composition epoxy resin preferably exists with more amount, as long as moldability is not subjected to harm.Per 100 parts by weight of component of amount (A), (B) and the mixture (D) that load mineral filler (C) are preferably 200-1,200 weight parts, more preferably 500-1,000 weight part.When filler less than 200 parts, composition may have the coefficient of expansion that multiple pressure power is more put on the semiconducter device of encapsulation, may damage device performance.Filler surpasses 1,200 part of mobile and overslaugh mold pressing that may reduce composition significantly.
In order to increase the bond strength between resin and the mineral filler, the mineral filler of Shi Yonging is here preferably carried out pre-treatment with coupling agent to the surface.Suitable coupling agents is silane and titanate coupling agent.In these coupling agents, the preferred silane coupling agent for example comprises epoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-epoxypropoxy methyldiethoxysilane, and β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane; Aminosilane is N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan for example, γ-An Bingjisanyiyangjiguiwan and N-phenyl-γ-An Bingjisanjiayangjiguiwan; With hydrosulphonyl silane γ-hydrosulphonyl silane for example.Not to being used for surface-treated coupling agent consumption or the surface-treated method is carried out particular determination.
Being included in (D) in the semiconductor packages fire retarded epoxy resin composition of the present invention and being fusing point and be 110 ℃-130 ℃ average group becomes the phosphazene compound of general formula (1),
Subscript a wherein, b and n satisfy 0＜a≤0.05n, 1.90n≤b＜2n, 2a+b=2n and 3≤n≤6.
In the general formula (1), n is 3-6, preferably equals 3.General formula (1) phosphazene compound of preferred n=3 accounts for the 90wt% at least of whole phosphazene compound weight, that is to say, the ratio of n=3 is 90wt% at least.Subscript a, b and n satisfy 0＜a≤0.05n, the numeral of 1.90n≤b＜2n and 2a+b=2n.
If 0.05n＜a, because more crosslinked between polymolecular, phosphazene compound has higher softening temperature, and thereby with the compatibility variation of Resins, epoxy, can not reach desired flame retardant effect.The ratio of a is preferably 0.005n≤a≤0.05n.The ratio of b is preferably 1.90n≤b≤1.99n.
Desirably, in order to remove impurity (for example phosphoric acid and muriate), the phosphazene compound of general formula (1) is carried out recrystallize.By recrystallize, along with the alternative highly crystalline compound that obtains n=3 of the increase of product fusing point.The illustrative quality, Fig. 1 and 2 is respectively and does not have the phosphazene compound of recrystallize SPE-100 that (Otsuka Chemical Co. is Ltd) with the GPC figure of identical material recrystallize product.Molecular weight distribution is by the peak area decision of GPC figure.By the recrystallize of SPE-100, the ratio of the compound of n=3 rises to 90wt% or higher from 72wt%.Simultaneously, from the DSC of Fig. 3 and 4 figure as can be seen, fusing point rises to 114 ℃ from 108 ℃.
Recrystallize also is that effectively wherein this phosphate ion can extract from phosphonitrile with hot water for the amount that reduces total phosphate ion.Then, compare with add phosphine flame retardant (as red phosphorus and phosphoric acid salt) in composition epoxy resin, the semiconductor packages fire retarded epoxy resin composition that adds general formula (1) phosphazene compound provides a kind of solidifying product with water hot extraction's performance and significantly improved moisture-proof reliability of improvement.It is to be noted according to following definite total phosphate ionic amount.Composition epoxy resin is 175 ℃ in temperature, and molding pressure is that 6.9N/mm2 and molding cycle are 120 seconds, and under 4 hours condition of 180 ℃ of following secondary hardenings, being molded into diameter is 50mm, and thickness is the pan of 3mm.On disc refiner, pan is worn into particle, therefrom collect the 10g particle size and be part particle from 50-212 μ m.This powder is partly joined in the 50ml pure water, and heating extracted in 20 hours under 125 ℃.Finally, with the total phosphate ionic concn in the ICP spectral measurement filtrate.The total phosphate ionic concn that semiconductor packages fire retarded epoxy resin composition of the present invention is measured under these conditions is preferably until 20ppm, more preferably until 10ppm.
Use suitable solvent to carry out recrystallize by the phosphazene compound of ordinary method mutual-through type (1).The solvent that is used for recrystallize is not crucial, if they be can the dissolved phosphorus nitrile compound rich solvent and the combination of poor solvent that can not the dissolved phosphorus nitrile compound.Suitable rich solvent comprises for example for example benzene, toluene and dimethylbenzene of acetone and methyl iso-butyl ketone (MIBK) (MIBK) and aromatic hydrocarbons of ketone.Suitable poor solvent comprises aliphatic hydrocarbon (for example hexane) and alcohol (for example methyl alcohol and ethanol).The solvent that is used for recrystallize should desirably comprise less impurity.
Suitable phosphazene compound (D) add-on is 1-50wt%, and more preferably 2-20wt% is based on component (A), (B) and gross weight (D).Phosphazene compound can not reach desired flame retardant resistance less than 1wt%, yet phosphazene compound surpasses the flowability that 50wt% may reduce composition.
Composition epoxy resin of the present invention can comprise the molybdenum component that contains zinc molybdate of mineral filler support, as additional fire retardant.Molybdenum component is used in combination with phosphazene compound (D) and has obtained higher levels of flame retardant resistance, and has reduced the consumption of phosphazene compound (D).Molybdenum component can also be captured enemy personnel agent as ion.
Support the suitable mineral filler of zinc molybdate to comprise silicate (for example fused silica and crystalline silica), talcum, alumina, silicon nitride, aluminium nitride, boron nitride, titanium dioxide, zinc oxide and glass fibre.The mineral filler mean particle size is preferably at 0.1-40 μ m, and more preferably 0.5-15 μ m and specific surface area are 0.5-50m
2/ g, more preferably 0.7-10m
2/ g.It should be noted that and to determine mean particle size by for example weighted mean or the median particle diameter of laser diffraction technology mensuration mean particle size, and determine specific surface area by for example BET adsorption method.
In the molybdenum component of the zinc molybdate that has mineral filler to support, zinc molybdate content is preferably 5-40wt%, more preferably 10-30wt%.Zinc molybdate content still less can not provide satisfied flame retardant resistance, however the too high levels overslaugh flowing at molding and setting up period.
The molybdenum component that is present in the mineral filler with the zinc molybdate form is can be from Sherwin-Williams Co with trade(brand)name KEMGARD 1260,1261, and 911B and 911C are purchased.
Mixing the suitable amount of molybdenum component is the 3-100 weight part, and preferred 5-100 weight part is based on 100 parts by weight of component (A), (B) and mixture (D).Satisfied flame retardant resistance be can not provide less than 3 parts molybdenum components, mobile and curing performance damaged yet surpass 100 parts.The molybdenum component add-on that contains the zinc molybdate of mineral filler support is the zinc molybdate that the combination of per 100 weight part Resins, epoxy and solidifying agent exists 0.1-40 part, particularly 0.2-40wt%.Zinc molybdate less than 0.1 weight part can not provide satisfied flame retardant resistance, yet has destroyed mobile and curing performance above the zinc molybdate of 40 weight parts.
The fire-retardant composition epoxy resin of semiconductor packages of the present invention can further comprise other fire retardant, for example oxyhydroxide such as aluminium hydroxide and magnesium hydroxide, mineral compound is zinc borate and zinc for example, and silicon resin compound, as long as objects and advantages of the present invention do not suffer damage.It should be noted that not comprise antimony compounds, for example antimonous oxide.Equally preferably, do not comprise phosphine flame retardant, for example red phosphorus and phosphoric acid salt (being different from phosphazene compound).
If necessary, composition epoxy resin of the present invention can also comprise multiple additives, only otherwise infringement the object of the invention gets final product.Illustrative example comprises the additive that reduces stress, as thermoplastic resin, and thermoplastic elastomer, synthetic organic rubber and organosilicon polymer; Wax, as carnauba wax, higher fatty acid and synthetic wax; Tinting material is as carbon black; Capture enemy personnel agent with halogen.
Can be by mixed Resins, epoxy, solidifying agent, mineral filler, phosphazene compound and selectable additive to be predetermined, in mixing tank or other proper device, mix these components up hill and dale, use fusing such as hot roll mill, kneading machine, extrusion machine then and handle the mixture that obtains, prepare composition epoxy resin of the present invention as moulding material.Then, the mixture of cooling process also solidifies, and wears into suitable size then to obtain moulding material.
Synthetic composition epoxy resin of the present invention can be used for packaging various semiconductor devices effectively.Usually the method for packing that uses at most is the low pressure transfer moudling.Composition epoxy resin of the present invention is preferably the 150-180 ℃ of about 30-180 of following molding second, then approximately carrying out the about 2-16 of secondary hardening hour under 150-180 ℃.
Semiconductor packages fire retarded epoxy resin composition of the present invention is molding effectively, and is solidified into the product with excellent flame retardancy and moisture-proof reliability.Composition does not have deleterious effect to HUMAN HEALTH and environment, because they do not comprise bromide (for example Resins, epoxy of bromination) and antimony compounds (for example antimonous oxide).Semiconducter device with Cured epoxy resin compositions encapsulation of the present invention keeps sufficient flame retardant resistance and moisture-proof reliability, thereby very valuable in industry.
Embodiment
In order further to illustrate the present invention, the following embodiment that provides embodiments of the invention and comparative example and preparation phosphazene compound together still is not to limit the present invention.All parts and percentage ratio are based on weight.
The preparation embodiment A
Initial reagent is that the fusing point of on average forming general formula (2) is 108 ℃ a phosphazene compound (from OtsukaChemical Co., the SPE-100 of Ltd., phosphorus atom content are 11.0%, and sulphur atom content is 0.14%).
In the general formula (2), a, b and n ' satisfy 0＜a≤0.05n ', 1.90n '≤b＜2n ', the number of 2a+b=2n ' and 3≤n '≤1000.In nitrogen atmosphere, SPE-100 is dissolved in the 225g toluene with the 100g phosphazene compound.After solution is even, drip hexane at leisure.Before this solution becomes white opacity, stop to add hexane at once.This solution can be kept in the refrigerator chamber.Leach the crystalline deposit thing, the mixture flushing with toluene and hexane extracts by lock out operation, and is dry in a vacuum then.Obtain the phosphazene compound (fusing point is 114 ℃) that 50g exists with white crystalline form.By x-ray fluorescence analysis, the phosphorus atom content of this compound is 11.6%, and sulphur atom content is 0.13%.
Fig. 1-4 has shown that phosphazene compound SPE-100 and its recrystallize (that is to say the compound that is obtained in the preparation embodiment A) obtain the GPC and the dsc analysis result of product afterwards.
Embodiment 1-4 and comparing embodiment 1-5
By even melting mixing component as shown in table 1, preparation is used for the composition epoxy resin of semiconductor packages in two roller mills of heat, then cools off and grinds.Measure composition properties by following method.
The result is presented in the table 2.
(1) helicoidal flow
Use is measured under following condition according to the specified mould of EMMI standard: 175 ℃ of temperature, mold pressing 6.9N/mm
2, clamp time is 120 seconds.
(ii) gelation time
Measure the gel time of composition epoxy resin on 175 ℃ hot plate as gelation time.
(iii) mold pressing hardness
According to JIS-K6911, at 175 ℃ and 6.9N/mm
2The rod that prepared 10 * 4 * 100mm under the pressure by the composition epoxy resin mold pressing in 90 seconds.Measure hardness with the Barcol hardness tester while hot.
The (iv) phosphate ion in the extraction water
Composition epoxy resin is 175 ℃ in temperature, and molding pressure is 6.9N/mm
2, molding cycle is 120 seconds, and under 4 hours condition of 180 ℃ of following secondary hardenings, being molded as diameter is 50mm, thickness is the pan of 3mm.On disc refiner, pan is worn into particle, therefrom collect the part particle of 10g particle size from 50-212 μ m.This powder is partly joined in the 50ml pure water, and its heating under 125 ℃ extracted in 20 hours.With the total phosphate ionic concn in the ICP spectral measurement filtrate.
(v) flame retardant resistance
According to the UL-94 standard, its flame retardant resistance of check behind the thick plate of 1.5875mm of mold pressing (1/16 inch).
(vi) wet fastness
6 * 6 millimeters the silicon substrate of being measured as that has on it that aluminum steel forms is bonded in 14 pin dual-in-line package (DIP) structures (alloy 42), and the aluminium electrode on the substrate surface uses the hot travel route wire bond of diameter 30 μ m on lead frame.Then on substrate with 175 ℃ temperature and 6.9N/mm
2Pressure mold pressing composition epoxy resin 120 seconds, 180 ℃ of following regelates 4 hours.Thus obtained 20 are packaged in 140 ℃, the air of RH85% and kept 500 hours, are subjected to simultaneously-bias voltage of 5V DC.Aluminium corrosive packing number appears in statistics.
(the vii) reliability under high-temperature storage
6 * 6 millimeters the silicon substrate of being measured as that has on it that aluminum steel forms is bonded in 14 pin dual-in-line package (DIP) structures (alloy 42), and the aluminium electrode on the substrate surface uses the hot travel route wire bond of diameter 30 μ m on lead frame.Then on substrate with 175 ℃ temperature and 6.9N/mm
2Pressure mold pressing composition epoxy resin 120 seconds, 180 ℃ of following post cures 4 hours.Thus obtained 20 are packaged in 200 ℃ of air and kept 500 hours.Use nitrosonitric acid to dissolve cured resin, thus the Kaifeng packing.Measure the tensile strength of hot travel route.It is unacceptable product that test back draft intensity is reduced to the sample that is lower than initial value 70%.Report the unacceptable product number of per 20 samples.
Table 1
| Prescription (pbw) | Embodiment | The comparative example | ||||||||
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | 4 | 5 | ||
| Resins, epoxy | 59 | 62 | 59 | 53 | 54 | 62 | 62 | 53 | 59 | |
| Solidifying agent | 33 | 36 | 33 | 27 | 38 | 38 | 36 | 27 | 33 | |
| Molybdenum component | 10 | 10 | 10 | 10 | ||||||
| Phosphazene compound | The compound of embodiment A preparation | 8 | 2 | 8 | 20 | |||||
| SPE-100 | 2 | 20 | 8 | |||||||
| Red phosphorus | 2 | |||||||||
| Brominated epoxy resin | 8 | |||||||||
| ANTIMONY TRIOXIDE SB 203 99.8 PCT | 10 | |||||||||
| Mineral filler | 600 | 600 | 600 | 600 | 600 | 600 | 600 | 600 | 600 | |
| Curing catalyst | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | |
| Releasing agent | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | |
| Carbon black | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | |
| Silane coupling agent | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | |
Resins, epoxy: o-cresol phenolic resin varnish, the EOCN1020-55 (epoxy equivalent (weight) 200) that provides by Nippon Kayaku Co Ltd
Solidifying agent: phenol novolac resin, the DL-92 (phenolic hydroxyl group equivalent 110) that provides by Meiwa Kasei K.K.
Molybdenum component: the zinc molybdate on sandwich layer, the KEMGARD 911C (zinc molybdate content 18wt%, the sandwich layer: the talcum of median size 2.0 μ m, specific surface area 2.0m that provide by Sherwin-Williams Co
2/ g)
Mineral filler: by the spherical fused silica (median size 20 μ m) of Tatsumori K.K production
Curing catalyst: the DBU that provides by Sun Apollo K.K
Releasing agent: the carnauba wax that provides by Nikko Fine Products K.K
Carbon black: the Denka Black that provides by Denki Kagaku Kogyo K.K
Silane coupling agent: the KBM403 (γ-glycidoxypropyltrime,hoxysilane) that provides by shin Etsu Chemical Co.Ltd.
Table 2
| Test result | Embodiment | The comparative example | |||||||
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | 4 | 5 | |
| Helicoidal flow (cm) | 85 | 80 | 83 | 85 | 83 | 83 | 80 | 85 | 85 |
| Gelation time (second) | 17 | 17 | 17 | 19 | 17 | 17 | 17 | 19 | 17 |
| Mold pressing hardness | 85 | 88 | 84 | 80 | 84 | 88 | 83 | 80 | 85 |
| Phosphate ion in the extraction water (ppm) | 1 | ＜1 | 1 | 5 | 1 | 200 | 17 | 30 | 24 |
| Flame retardant resistance | V-1 | V-1 | V-0 | V-0 | V-0 | V-0 | Burning weakens | V-0 | V-0 |
| Wet fastness | 0/20 | 0/20 | 0/20 | 0/20 | 0/20 | 20/2 0 | 0/20 | 10/20 | 8/20 |
| Reliability under high-temperature storage | 0/20 | 0/20 | 0/20 | 0/20 | 20/20 | 0/20 | 0/20 | 0/20 | 0/20 |
Find out obviously that from table 2 semiconductor encapsulating epoxy resin composition of the present invention is by mold pressing effectively and be solidified into product, but this product have excellent flame retardancy and moisture-proof and the anti-reliability of phosphoric acid extraction salt ion on a small quantity.Use the semiconducter device of composition epoxy resin encapsulation of the present invention to keep sufficient fire retardant and moisture-proof reliability.Because do not comprise for example Resins, epoxy of bromination and antimony compounds ANTIMONY TRIOXIDE SB 203 99.8 PCT for example of bromide, composition does not have harmful effect to HUMAN HEALTH and environment.
Claims (5)
1. a semiconductor packages fire retarded epoxy resin composition comprises main ingredient,
(A) Resins, epoxy,
(B) phenolic resin curative, its consumption make in this solidifying agent that the molar ratio range of epoxy group(ing) is 0.5-1.5 in the phenolic hydroxyl group and Resins, epoxy,
(C) mineral filler, per 100 parts by weight of component (A), (B) and (D) consumption in the mixture be the 200-1200 weight part and
(D) on average form the phosphazene compound of general formula (1), fusing point is 110-130 ℃, its consumption based on component (A), (B) and (C) gross weight count 1-50wt%,
Wherein descend target a, b and n to satisfy 0＜a≤0.05n, 1.90n≤b＜2n, the numeral of 2a+b=2n and 3≤n≤6, the ratio of n=3 is at least 90wt%, and composition is substantially free of bromide and antimony compounds.
2. the composition epoxy resin of claim 1 wherein obtains the phosphazene compound of general formula (1) by recrystallize.
3. the composition epoxy resin of claim 1 further comprises molybdenum component, has the zinc molybdate of supporting in mineral filler.
4. any one composition epoxy resin of claim 1-3, wherein when using water hot extraction's composition, the phosphate ion concentration in the extraction water is until 20ppm.
5. a cure states semiconducter device uses any one the composition epoxy resin encapsulation of claim 1-4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002297352A JP2003268208A (en) | 2002-01-11 | 2002-10-10 | Flame retardant epoxy resin composition for sealing of semiconductor and semiconductor device |
| JP2002297352 | 2002-10-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1497714A CN1497714A (en) | 2004-05-19 |
| CN1302070C true CN1302070C (en) | 2007-02-28 |
Family
ID=32064183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031602789A Expired - Fee Related CN1302070C (en) | 2002-10-10 | 2003-08-01 | Flame-retarded epoxy composition for packing semiconductor and semiconductor device |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US7122587B2 (en) |
| KR (1) | KR100584069B1 (en) |
| CN (1) | CN1302070C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005120228A (en) * | 2003-10-16 | 2005-05-12 | Nitto Denko Corp | Epoxy resin composition for optical semiconductor element sealing and optical semiconductor device using the composition |
| US7332069B2 (en) * | 2004-04-28 | 2008-02-19 | E.I. Du Pont De Nemours & Co. | Cathodic corrosion protection powder coating composition and method |
| KR101194498B1 (en) * | 2005-04-04 | 2012-10-25 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Flame Retardant and an Epoxy Resin Composition comprising the Same for Encapsulating Semiconductor Device |
| US8048969B2 (en) * | 2005-04-25 | 2011-11-01 | Shin-Etsu Chemical Co., Ltd. | Semiconductor encapsulating epoxy resin composition and semiconductor device |
| JP4901687B2 (en) * | 2007-10-17 | 2012-03-21 | 日東電工株式会社 | Photosensitive resin composition and flexible printed circuit board having insulating cover layer obtained using the same |
| CN104497493A (en) * | 2015-01-15 | 2015-04-08 | 江苏恒神纤维材料有限公司 | Formula for pollution-free organic fertilizer and preparation method thereof |
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| JP2001329142A (en) * | 2000-05-22 | 2001-11-27 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2001335679A (en) * | 2000-05-29 | 2001-12-04 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semi-conductor device |
| JP2001354840A (en) * | 2000-06-15 | 2001-12-25 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2001354839A (en) * | 2000-06-15 | 2001-12-25 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2002012741A (en) * | 2000-06-27 | 2002-01-15 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2002037977A (en) * | 2000-07-24 | 2002-02-06 | Toshiba Chem Corp | Sealing resin composition and semiconductor-sealing device |
| JP2002037978A (en) * | 2000-07-24 | 2002-02-06 | Toshiba Chem Corp | Sealing resin composition and semiconductor-sealing device |
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| JPS55136105A (en) * | 1979-04-07 | 1980-10-23 | Otsuka Chem Co Ltd | Production of cyclic phosphazene oligomer |
| JP2843244B2 (en) | 1993-12-08 | 1999-01-06 | 住友ベークライト株式会社 | Epoxy resin composition |
| JP3783312B2 (en) | 1997-01-17 | 2006-06-07 | 日立化成工業株式会社 | Epoxy resin molding material for electronic component sealing and electronic component |
| CA2275247C (en) * | 1997-10-15 | 2005-01-11 | Otsuka Chemical Co., Ltd. | Crosslinked phenoxyphosphazene compounds, flame retardant, flame-retardant resin compositions, and moldings of flame-retardant resins |
| JP2001192535A (en) * | 2000-01-11 | 2001-07-17 | Toshiba Chem Corp | Resin composition for sealing and sealed semiconductor device |
| JP3489025B2 (en) * | 2000-01-14 | 2004-01-19 | 大塚化学ホールディングス株式会社 | Epoxy resin composition and electronic component using the same |
| JP2001316565A (en) * | 2000-05-10 | 2001-11-16 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2001329143A (en) * | 2000-05-22 | 2001-11-27 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2001329144A (en) * | 2000-05-22 | 2001-11-27 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2002047393A (en) * | 2000-08-01 | 2002-02-12 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP5318306B2 (en) * | 2001-02-09 | 2013-10-16 | 東洋紡株式会社 | Heat resistant composition |
| JP2003226796A (en) * | 2002-02-07 | 2003-08-12 | Shin Etsu Chem Co Ltd | Flame-retardant epoxy resin composition for sealing semiconductor, and semiconductor device |
-
2003
- 2003-07-30 KR KR1020030052586A patent/KR100584069B1/en active IP Right Grant
- 2003-08-01 CN CNB031602789A patent/CN1302070C/en not_active Expired - Fee Related
- 2003-08-12 US US10/638,337 patent/US7122587B2/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001329142A (en) * | 2000-05-22 | 2001-11-27 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2001335679A (en) * | 2000-05-29 | 2001-12-04 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semi-conductor device |
| JP2001354840A (en) * | 2000-06-15 | 2001-12-25 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2001354839A (en) * | 2000-06-15 | 2001-12-25 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2002012741A (en) * | 2000-06-27 | 2002-01-15 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2002037977A (en) * | 2000-07-24 | 2002-02-06 | Toshiba Chem Corp | Sealing resin composition and semiconductor-sealing device |
| JP2002037978A (en) * | 2000-07-24 | 2002-02-06 | Toshiba Chem Corp | Sealing resin composition and semiconductor-sealing device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100584069B1 (en) | 2006-05-29 |
| KR20040032736A (en) | 2004-04-17 |
| US20040072968A1 (en) | 2004-04-15 |
| CN1497714A (en) | 2004-05-19 |
| US7122587B2 (en) | 2006-10-17 |
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